Benz-{8 c,d{9 -indolium dyestuffs

ABSTRACT

Cationic dyestuffs having one of the groups or WHEREIN R1 and R2 denote hydrogen, an alkyl, cycloalkyl, aralkyl, aryl or amino radical or a heterocyclic ring, R3 denotes an alkyl, cycloalkyl or aralkyl radical, and R3 can be bonded to R1 or R2, are adapted for the use in dyeing and printing natural and synthetic materials.

United States Patent [191 Brack et al.

[ BENZ-[ C,D]-INDOLIUM DYESTUFFS [75] Inventors: Alfred Brack; Hubertus Psaar, both of Leverkusen, Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany [22] Filed: June 8, 1972 [21] Appl;No.: 260,914

[30] Foreign Application Priority Data June 8, 1971 Germany 2128326 [52] U.S. Cl 260/326.9, 260/309.2, 260/310 C, 260/310 D, 260/313.1, 260/314.5, 260/335,

260/556 AR, 260/556 R, 8/3. 8/542,

260/279 R, 260/283 SA. 260/294.8 E, 6 2.1 qlloemrs R [51] Int. Cl C07d 27/44 [58] Field of Search 260/240 B, 313.1, 326.9

[56] References Cited UNITED STATES PATENTS 2,337,909 12/1943 Martin et a1. 260/397.7 R 3,347,865 10/1967 Brack et al. 260/3131 FOREIGN PATENTS OR APPLlCATlONS 2,018,863 6/1960 France 260/313.1

[ Dec. 10, 1974 OTHER PUBLICATIONS Northey et al., The Sulfonamides and Allied Compounds, Frontispage and page 104, Reinhold Pub. Corp. N.Y., (1948).

Northey et 211., J. Am. Chem. Soc. vol. 64, pages 2763 to 2765, (1942).

Primary Examiner-John D. Randolph Attorney, Agent, or FirmPlumley & Tyner [5 7 ABSTRACT Cationic dyestuffs having one of the groups 2 Claims, No Drawings 1 BENZ-[C,D]-INDOLIUM DYESTUFFS The subject of the invention are new cationic dyestuffs of the general formula wherein F denotes the radical of a cationic dyestufi, B denotes a direct bond or a linking member, n denotes the numbers 1, 2, 3 or 4, m denotes the numbers 1 or 2, Z denotes the groupings 1 R denotes hydrogen, an alkyl, cycloalkyl, aralkyl or la L.

clammonium salts of which the colour is attributable to the delocalisation of the charge in the chromophoric system. a

Preferred dyestuffs are those of the general formula wherein Dyestuffs to be singled out are those of the general formula III wherein R denotes hydrogen or an alkyl, cycloalkyl, aralkyl or aryl radical, K denotes the groupings aryl radical, a disubstituted amino group or a heter- R ocyclic ring, -AN R --A-O-R R denotes hydrogen, an alkyl, cycloalkyl, aralkyl or 5 aryl radical or an optionally substituted amino group or a heterocyclic ring, I

R R R R J C R c A e -c- 0-11 E II I and R -o-N N" c R N (Hi 15 7 \N 10 R l R denotes an alkyl, cycloalkyl or aralkyl radical,

R can be bonded to R or to R by a direct bond or 5 by a hetero-atom and Andenotes an anion, and

the radical Z can be linked directly or via the bridge member B to a C-atom or an aromatic-carbocyclic or aromatic-heterocyclic ring of the cationic dye- 60 stuff.

The cationic dyestuffs can belong, for example, to the azo, anthraquinone, phthalocyanine. phthaloperinone. quinophthalone, formazane, azine, acridine, diarylmethane, and triarylmethane, xanthene, methine (including the various azamethine types), azomethine, hydrazone and nitro dyestuff series. Cyclammonium salts are preferred, and here again those of the methine series in the widest sense are preferred, that is to say cy- A denotes an aromatic ring,

A denotes a direct bond or an aromatic ring,

R, denotes hydrogen or an alkyl, cycloalkyl, aralkyl or aryl radical,

R denotes an alkyl, cycloalkyl, aralkyl or aryl radical,

R denotes an alkyl, cycloalkyl, aralkyl or aryl radical,

R denotes a styryl, aryl or heteryl radical,

R and R denote hydrogen or an alkyl, aralkyl or cycloalkyl or aryl radical,

R and R denote hydrogen or an alkyl radical,

R denotes an alkyl, cycloalkyl, aralkyl, aryl or heteryl radical,

R denotes hydrogen or an alkyl, cycloalkyl, aralkyl,

aryl or heteryl radical or-an alkoxy or alkoxycarbonyl group,

R denotes hydrogen or an alkyl, azalkyl or aryl radical and D denotes the remaining members of a S-membered or 6-membered nitrogen-containing ring,

R,,andR,orA,R,;andA,R andR ,R orR and R and R and R can be bonded by a direct bond or by a hetero-atom and B, Z and An have the abovementioned meaning and R, can be bonded to the naphthalene ring and E represents the remaining members of I a membered or 6-membered ring.

Particularly preferred dyestuffs amongs these are those of the general formula wherein and of, esters of phosphoric acid, such as of methyl phosphate.

R denotes hydrogen or an alkyl or aralkyl radical,

R denotes hydrogen or an alkyl, cycloalkyl, aralkyl or aryl radical,

R denotes an alkyl, aralkyl or aryl radical,

R denotes an alkyl radical R denotes an alkyl, aralkyl, aryl or heteryl radical,

B and An have the meaning already indicated and R and the naphthalene ring, R and the phenylene ring or R and R and R and R can be linked by a direct bond or by a hetero-atom. Suitable linking members B are, for example, saturated or unsaturated C,C -hydrocarbon radicals, preferably C, C,-hydrocarbon radicals, such as methylene, ethylene l,3-propylene, l,4-butylene, hexamethylene or dekamethylene radicals, vinylene or allylene radicals, a hetero-atom such as nitrogen, oxygen, sulphur or phosphorus or a combination of one or more hetero-atoms witih such hydrocarbon radicals. The

linking member can also contain non-ionic substituents.

Possible anionic radicals An are the organic and inorganic anions which are customary in cationic dyestuffs.

inorganic anions are, for example, fluoride, chloride,

bromide and iodide, perchlorate, hydroxyl, radicals of acids containing 8, such as hydrogen sulphate, sulphate, disulphate and aminosulphate; radicals of nitrogen'oxygen acids, such as nitrate; radicals ofoxygenacids of phosphorus, such as dihydrogen phosphate, hy- 6Q Organic anions are, for example, anions of saturated or unsaturated aliphatic, cycloaliphatic, aromatic and heterocyclic carboxylic acids and sulphonic acids, such as radicals of acetic acid, chloroacetic acid, cyanoacetic acid, hydroxyacetic acid, aminoacetic acid, methylaminoacetic acid, aminoethyl-sulphonic acid. methylaminoethyl-sulphonic acid, propionic acid, nbutyric acid, i-butyric acid, 2-methyl-butyric acid, 2- ethyl-butyric acid, dichloroacetic acid, trichlororacetic acid, trifluoroacetic acid, 2-chloropropionic acid, 3- chloropropionic acid, 2-chlorobutyric acid, 2-hydroxypropionic acid, 3-hydroxypropionic acid, v O- ethylglycollic acid, thioglycollic acid, glyceric acid,

tetravanadate, molybdate, tungstate, chromate, bichromalic acid, dodecyltetraethyleneglycol-ether-propionic acid, 3-(nonyloxy)-propionic acid, 3-(isotridecyloxy) propionic acid, 3-(isotridecyloxy)-diethyleneglycolether-propionic acid, the ether-propionic acid of the alcohol mixture with 6 to 10 carbon atoms, thioacetic acid, 6-benzoylarnino-2-chlorocaproic acid, nonylphenoltetraethyleneglycol-ether-propionic acid, nonylphenoldiethyleneglycolether-propionic acid, dodecyltetraethyleneglycol-ether-propionic acid, phenoxyacetic acid, nonylphenoxyacetic acid, n-valeric acid, i-valeric acid, 2,2,2-trimethylacetic acid, n-caproic acid, 2- ethyl-n-caproic acid, stearic acid, oleic acid, ricinoleic acid, palrnitic acid, n-pelargonic acid, lauric acid, a mixture of aliphatic carboxylic acids with 9 to ll carbonatoms (Versatic Acid 9ll of SHELL), a mixture of aliphatic carboxylic acids with 15 to 19 carbon atoms (Versatic Acid 1519 of SHELL), coconut fatty acid first runnings, undecanecarboxlyic acid, ntridecanecarboxylic acid and a coconut fatty acid mixture; acrylic acid, methacrylic acid, crotonic acid, propargylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azaleic acid, the isomer mixture of 2,2,4- and 2,4,4- trimethyladipic acid, sebacic acid, isosebacic acid (isomer mixture), tartaric acid, citric acid, glyoxylic acid, dimethyl-ether-a,a' dicarboxylic acid, methylenebisthioglycollic acid, dimethylsulphide-oi,oz-dicarboxylic' acid, 2,2 5-dithio-di-n-propionic acid, fumaric acid, maleic ac1d,itaconic acid, ethylene-bis-iminoacetic acid,

nitrilosulphonic acid, methanesulphonic acid, ethanesulphonic acid, chloromethanesulphonic acid, Z-chloroethanesulphonic acid and Z-hydroxyethanesulphonic acid, and mersolate, that is to say C C, -paraffinsulphonic acid, obtained by chlorosulphonation of paraffin oil.

Suitable anions of cylcoaliphatic carboxylic acids are, for example, the anions of cyclohexanecarboxylic acid and cyclohexene-3-carboxylic acid and anions of araliphatic monocarboxylic acids are, for example, anions of phenylacetic acid, 4-methylphenylacetic acid and mandelic acid.

Suitable anions of aromatic carboxylic acids are, for example, the anions of benzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 4- tert.-butylben2oic acid, 2-bromobenzoic acid, 2- chlorobenzoic acid, 3-chlorobenzoic acid, 4- chlorobenzoic acid, 2,4-dichlorobenzoic acid, 2,5- dichlorobenzoic acid, 2-nitrobenzoic acid, 3- nitrobenzoic acid, 4-nitrobenzoic acid, 2-chloro-4- nitrobenzoic acid, 6-chloro-3-nitro-benzoic acid, 2,4- dinitrobenzoic acid, 3,4-dinitrobenzoic acid, 3,5- dinitrobenzoic acid, Z-hydroxybenzoic acid, 3- hydroxybenzoic acid, 4-hydroxybenzoic acid, 2- mercaptobenzoic acid, 4-nitro-3-methylbenzoic' acid, 4-aminobenz0ic acid, 5-nitro-2-hydroxybenzoic acid, 3-nitro-2hydroxybenzoic acid, 4-methoxybenzoic acid, 3-nitro-4methoxybenzoic acid, 4-chloro-3- hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 5-chloro-2-hydroxy-3-methylbenzoic acid, 4- ethylmercapto-2-chlorobenzoic acid, 2-hydroxy-3- methylbenzoic acid, 6 hydroxy-3-methylbenzoic acid, 2-hydroxy-4-methylbenzoic acid 6-hydroxy-2,4- dimethylbenzoic acid, 6-hydroxy-3-tert.-butylbenzoic acid, phthalic acid, tetrachlorophthalic acid, 4- hydroxyphthalic acid, 4-methoxyphthalic acid, isophthalic acid, 4-chloroisophthalic acid, S-nitroisophthalic acid, terephthalic acid, nitroterephthalic acid and diphenyl-3,4-carboxylic acid, o-vanillic acid, 3-sulphobenzoic acid, benzene-l,2,4,5-tetracarboxylic acid, naphthalenel ,4,5 ,8-tetracarboxylic acid, biphenyl-4-carboxylic acid, abietic acid, phthalic acid mono-n-butyl ester, terephthalic acid monomethyl ester, 3-hydroxy-5,6,7,8-tetrahydronaphthalene-2- carboxylic acid, 2-hydroxy-l-naphthoic acid and antraquinone-2-carboxylic acid.

Suitable anions of heterocyclic carboxylic acids are, for example, the anions of pyromucic acid, dehydromucic acid and indolyl-3-acetic acid.

Suitable anions of aromatic sulphonic acidsare, for example, the anions of benzenesulphonic acid, benzene-1,3-disulphonic acid, 4-chlorobenzenesulphonic acid, 3-nitrobenzenesulphonic acid, 6-chloro-3- nitrobenzenesulphonic acid, toluene-4-sulphonic acid,

toluene-Z-sulphonic acid, toluene-sulphonic acid, 2-chlorotoluene-4-sulphonic acid, l-hydroxybenzenesulphonic acid, n-dodecylbenzenesulphonic acid, 1,2,- 3,4-tetrahydronaphthalene-6-sulphonic acid, naphthalenel -sulphonic acid, naphthalenel ,4- disulphonic acid or naphthalene-1,5-disulphonic acid, naphthalene-l ,3,5-trisulphonic acid, l-naphthol-Z- sulphonic acid, 5-nitronaphthalene-2-sulphonic acid, 8-aminonaphthalene- 1 -sulphonic acid, stilbene-2,2 disulphonic acid and biphenyl-Z sulphonic acid.

a s uitable atnion of heterocyclic sulphonic acids is, for example, the anion of quinoline-S-sulphonic acid.

Further possibilities are the anions of arylsulphinic, arylphosphonic and arylphosphonous acids, such as .benzenesulphinic and benzenephosphonic acid.

By an alkyl radical, there is understood a saturated or olefinically unsaturated aliphatic radical with 1 to 6 C atoms, which can contain non-ionic substituents and/or carboxyl groups, for example the methyl, ethyl, nand iso-propyl, nand isoand tert. butyl and the various isomeric pentyl and hexyl radicals, as well as vinyl, allyl or propenyl radicals.

Cycloalkyl radicals denote, for example, cyclopentyl and cyclohexyl radicals which can be substituted by nonionic radicals and/or carboxyl groups.

Aryl radicals are, for example, phenyl radicals which may be substituted by non-ionic substituents and/or by carboxyl groups, and their ring-fusion products, such as the naphthalene radical which may be substituted by non-ionic substituents and/or by carboxyl groups.

Aralkyl radicals are, for example, alkyl radicals substituted by aryl or heteryl radicals.

Heteryl radicals are S-membered or 6-membered unsaturated heterocyclic rings, such as the thienyl, pyridyl, pyrrolyl, indolyl-2, indolyl-3, benzthiazolyl-2 or benzoxazolyl-Z radical.

Non-ionic substituents in the sense of the present invention are the non-dissociating substituents which are customary in dyestuff chemistry, such as halogen, alkyl, cycloalkyl, hydroxyl, alkoxy, aralkoxy, cycloalkoxy, aryloxy, acyloxy, acylalkoxycarbonyl, amidocarbonyl, nitrile, nitro, amino, alkylamino, dialkylamino, acylamino, sulphonylamino, sulphonyl, amidosulphonyl, mercapto, alkylmercapto and arylmercapto groups.

The most valuable of the preferred dyestuffs of the formula IV are those of the formulae V to IX.

/R2O (O 25 N\RI 26 I An R H o s-N=cH-N 22 V R24-N cQ-n 0Q An(') VII VIII

R o s-n=cH-N 22 2 23 1 0H O S-N=CH-N 3 J CH wherein C -alkoxy-ethyl group or an aralkyl radical and R R R, andAnhave the meaning already indicated, denotes a methyl or ethyl group, and the quoted number of C atoms of the lower alkyl radicals re- Rm denotes hydrogen or an alkyl radical with 1 to 4 lates to the uninterrupted carbon chain of the alkyl C atoms, radical, excluding possible carbon-containing sub- R denotes an alkyl radical with l to 4 C atoms or stituents, and the lower all yl radicals, the naphthaa phenyl radical, 40 lene ring, the p-phenylene ring which represents A, the R denotes an alkyl radical with 1 to 4 C atoms or phenyl radical which represents R and the aralkyl rada phenyl radical, ical which represents R can be substituted by non- R denotes an alkyl radical with l to 4 C atoms or ionic substituents and/or carboxyl groups.

together with R and the N-atom represents a pyr- Further particularly valuable dyestuffs are those of rolidine, piperidine, piperazine or morpholine ring, the formula 22 x Q S-N=CH-N 1' denotes an alkyl radical with l to 5 C atoms, wherein R denotes a methyl, ethyl, n-propyl, n-butyl, R22, R 3, R and An have the meaning already indi- B-alkoxycarbonyl-, B-cyano-, B-chloroor B-C -C cated, alkoxyethyl group, R represents a methyl, ethyl, n-propyl, n-butyl. n- R denotes a methyl, ethyl, n-propyl, n-butyl, y YL fly y B- YL B- y- 9 10 alkoxycarbonyl)-ethyl, B-amidocarbonylethyl or products consisting of these materials and dyed, (C -C )-alkoxycarbonylmethyl group and printed and/or bulk-dyed with the dyestuffs according R represents hydrogen or a methyl, ethyl, methoxy, to the invention.

ethoxy, nand iso-propoxy, nand iso-butoxy, or A further object of the present application are probenzyloxy group. 5 cesses for the manufacture of dyestuffs of the formulae Amongst these dyestuffs those of the formula Ito Xla, which are characterised in that in cationic dyeg./ N R H) "77"" 50 R 27 An XI CH SN=CH-N CH 2O wherein stuffs or dyestuff intermediate products at least one R and An have the meaning already indicated, group Z, which has the meaning indicated in the for- R' independently of R also denotes a methyl or mula (I), is introduced in accordance with processes ethyl group and which are in themselves known and that in the case of R denotes hydrogen or a methoxy or ethoxy group, the introduction into intermediate products, these are preferred. products are then converted, in a manner which is in Furthermore, dyestuffs of the formula itself known, into cationic dyestuffs.

, R24 N C g Q R50 51 XIa R An O S-N=C-N 2 l R R 3 wherein Dyestuffs of the formula (III) are obtained, for exam- R R R R24, R and An" have the meaning alpie, by condensation of intermediate products of the ready indicated and formula R represents hydrogen, a lower alkyl or alkoxy group with l to 4 C atoms, an acylamino or a sul R N C D phonylamino group, XII are particularly valuable. i

A further object of the present application are processes for dyeing, printing and bulk dyeing synthetic materials of polymerised unsaturated nitriles, such as polyacrylonitrile or vinylidene cyanide, acid-modified or XIII polyesters and acid-modified polyamides, as well as the especially those of the formula fluoride, it also being possible to dispense with the condensation agent when using a compound XIII or Xlll a.

A further subject of the invention is the conversion of those cationic dyestufis which are salts of proton acids and contain n-groups --B-Z, into the dyestuff bases from which they are derived, and their quatemisation by treatment with the reagents known for this purpose, such as dimethyl sulphate and diethyl sulphate, toluene-(or benzene-) sulphonic acid methyl ester, ethyl ester, n-propyl ester, B-chloroethyl ester, B-cyanoethyl ester, B-hydroxyethyl ester and B-ethoxyethyl ester, benzyl chloride, 4-methoxybenzyl chloride, allyl chloride and allyl bromide, B-dimethylaminoethyl chloride and B-chloro-(and bromo- )ethylpiperdine and -morpholine.

Processes which are particularly highlighted are those which are characterised in that compounds of the formula H-N C=D R-N C-X R 2 R 2 4-9 R 0 S-N=CN I: 2 l 3 l R An XIIa or XIIIa wherein 15 N CIX D represents oxygen, sulphur or a substituted amino group, X represents a radical which can be split off as an anion, and An represents an anion and wherein p Z B, Z, R, R R and K, have the meaning already indi 2 S414?- R cated, R 5 with compounds l(l-l, for example the compounds XIV-XVIII: wherem 11 $9 R H-A-N 4 H-A-O-R B R H-A -N 5 XV XIV N (II-R XVI $8 R C CH CH I I I! ll R /C N N R l R R 11 12 XVII 15 14 XVIII wherein 40 A, A, E and R to R have the meaning already indi- K, R1, R2 and s have the meanmg lr y Indicated, b t d, are treated with quatemising agents in the presence using a condensation agent which furnishes an anion or absence of an inert solvent. As inert solvents it An such as phosphorus oxychloride, phosphorus triis possible to use, for example, halogenated hydrochloride, phosphorus pentachloride, thionyl chloride, carbons, such as chlorobenzene, dichlorobenzene, tin tetrachloride, titanium tetrachloride and phsogene, methylene chloride, chloroform, carbon tetrachlooptionally with the addition of other agents which have n'de, ethylene chloride, tetrachlorethane, hydrothe effect of splitting off water, such as phosphorus carbons such as benzene, toluene, xylene or tetrapentoxide, aluminium chloride, zinc chloride or boron 5O lin or polar solvents such as nitrobenzene, nitromethane, dioxane, dimethylforrnamide methylpyrrolidone. A further subject of the invention are dyestuff intermediate products of the formula or N- R-N c=o 0 SN=C-N i 1 wherein R denotes hydrogen, or an alkyl, cycloalkyl, aralkyl or aryl radical,

R, denotes hydrogen, an alkyl, cycloalkyl, aralkyl or XXI R -N C=O R O S-N=CH-N 22 wherein R denotes hydrogen or an alkyl or aralkyl radical,

R denotes an alkyl radical with l to 4 C atoms or a phenyl radical and R denotes an alkyl radical with l to 4 C atoms or a phenyl radical or conjointly with R denotes a pyrrolidine, piperidine, piperazine or morpholine ring.

The introduction of the grouping Z into a dyestuff or into a dyestufi intermediate product can be effected as follows:

1. A sulphochloride of a cationic dyestuff or dyestuff intermediate product or another derivative of an appropriate sulphonic acid which reacts analogously is condensed with an amidine or guanidine.

2. A primary sulphonamide of a cationic dyestuff or dyestuff intermediate product is condensed with an active derivative of an amide or urea. Such active derivatives are, for example, acetals such as dimethylformamide-dimethyl-acetal, thio-compoundssuch as dimethylthioformamide and isothiuronium saltsfor example the adduct of dimethyl sulphate to tetrasubstituted thioureas-but above all the reaction products, known from the Vilsmeier reaction, with acid halides such as phosphorus oxychloride and phosgene, as well as adduets with alkylating agents such as dimethyl sulphate and toluenesulphonic acid esters.

3. According to w. Logemann and o. Artini, Chem.

Ber. 90, 2725 (1957).

4. According to C. Runti, L. Sindellari and F. Ulian. Aun, Chimica 50, 847 (1960).

Suitable amides or ureas are, for example, dimethyl-, diethyl-, di-n-propyl-, di-iso-propyl-, di-n-butyl-, di-isoamyl-, phenyl-methyl-, phenyl-ethyl-, phenyl-n-butyl-, methylcyclohexyl-, ethyl-BphenylethyL, di-B- phenylethyl-, methyl-,B-chloroethyb, methyl-B- cyanoethyl-, methyl-B-ethoxycarbonylethyl-, methyl-B- methoxyethyl-, di-B-chloroethyland di-B-methoxyethyl-formamide) N-formyl-, N-acetyl-, N-benzoyl-, N- phenacetyland N-dimethylamidocarbonylpyrrolidine, -piperdine, -morpholine and -piperazine, dimethyland diethyl-trimethylacetamide and -benzamide, tetramethyland tetraethyl-urea, N,N'carbonylbis-pyrrolidine, -piperidine and -morpholine, N- methyland N-ethyl-a-pyrrolidone and N-methyl-, N- ethyland N-benzyl-a-piperidone.

Suitable amidines and guanidines are the corresponding imino derivatives.

The introduction of the grouping Z into a dyestuff intermediate product can be combined with the subsequent conversion of this intermediate product into a cationic dyestuff, resulting in a one-pot process." This combination results particularly smoothly if the grouping Z is introduced according to (2), using a Vilsmeier complex.

Compounds of the formulae Xlla, Xllla and XIX suitable for the manufacture of the dyestuffs of the formulae l to Xl are listed in Tables 1, 2 and 3 below.

Table 1 Compounds of the formula XII a Methyl Oxygen Hydrogen Methyl Methyl Ethyl n-Propyl n n V iso-Propy1 n-Butyl iso-Butyl tert -Butyl n-Amyl iso-Amyl n i n nee-Pentyl g Ethyl Phenyl n u n 4-Me thoxyphenyl n n Ethyl Ethyl n n n-Butyl n-Butyl n n iso -Amyl iso -Ax nyl lflill m R D R R R Ethyl Oxygen Mebhyl Methyl He thyl Ethyl Dime thylamino N -P1peri dyl Pentame thylene Pentamethyl ene R Morpholinyl CH CH 0 CH CH CH CH 0 CH CH Sulphur Hydrogen Methyl Methyl Ph enylimino p-losylimino Oyclohexyl Oxygen n n B-Phenylethyl H II Benzyl n 4-Me thylbenz ene 4-Me thoxybenzene n u 4-Chlorobenzyl H u Phe nyl n n n 4-Me thyl-phenyl 4-Me thoxy -phenyl n B -Chloroethyl Oxygen Hydro gen Methyl Me thyl B-0yaLnoethyl B-Dimethylaminoethyl B-Ethoxycarbonylethyl Ethoxyc arbonylmethyl II n 6 --Me tho xyethyl Hyd rogen Sulphur Phenyl imino n B-Hyd roxyoarbonylethyl Oxygen Ethyl Tetramethylene n II Pentamethylene n n 11' 1| CH2 CH2 0 CH2 CH2 u n n u 2 CH2 1i cH2 CH2 CH -CH -CN Table 2 Compounds of the fonmula XIII a R X R R R An Methyl Mahylmercapto Hydrogen Methyl Methyl Methosulphate Ethyl do. do. do. do. y do. n-Propyl do. do. do. do. do. n-Butyl do. do. do. do. do. iso-Amyl do. do. do. do. do. B-C anocthyl do. do. do. do. do. B-Et oxyethyl do. do. do. do. do.

Phenyl do. do. do. do. do

Ethyl Chlorophosphoryloxy do. do. do. Chlonde do. C hlorocarbonyloxy do. do. do. do do. C hlorinc do. do do. do

Table 3 Compounds of the formula XIX 4Dimcthylamino-phenyl Hydrogen Methyl Methyl 4-Dicthylamino-phenyl do. do. do. 4-Di-n-propylamino-phenyl do. do. do. 4-N-Methyl-N-isobutyIamino-phenyl do. do. do. 4-N-Ethyl-N-B-hydroxycthyl-aminmphenyl do. do. do. 4-N-Iithyl-N-B-chlorocthyl-amino-phenyl do. do. do. 4-N-lithylN'B-cyanoethyl-amino-phenyl do. do. do. 4-DihcnZylamino phcnyl do. do. do. 4 N-Phcnyl-N-mcthyl-amino-phenyl do. do. do. 4N-Phenyl-N-cthyl-amino-phenyl do. do. do. 4-N-4-Methylphenyl-N-methyl-amino-phenyl do. do. do. 4-N-4-McthoxyphenyI-N-methyl-amino-phenyl do. do. do. 4-N-4-Ethoxyphenyl-N-methyl-amino-phenyl do. do. do. 4-N-4-Ethoxyphenyl-N-ethyl-amino-phenyl do. do. do. 3-Carbazol l do. do. do. 3-N-Methyl -carbazolyl do. do. do. 4-Ethoxy-phenyl do. do. do. 4-Phcnoxy-phenyl do. do. do. 3-lndolyl do. do. y do. 3-N Methyl-indolyl do. do. do. 3-N-Mcthyl-2-phenyl-indolyl do. do. do. 4-Dimethylamino-phenyl Meth I do. do.

do. Dimethylamino do. do. do. Hydrogen Pentamethylene Pentamethylenc do. do. Methyl Phenyl do. do. Ethyl do. do. do. do. Ethyl Suitable compounds of the formula XIV are, for example, N,N-dimethyl-, -diethyl-,-di-n-propyl-, -di-isopropyl-, di-n-butyl-, -di-isobutyl-, -di-n-pentyland di-n-hexyl-aniline, N-methyl-N-ethyl-, N-ethyl-N-nbutyl-, N-methyl-N-neopentyl-, N-iso-amyl-N-ethyl-, N-ethyl-N-B-chloroethyl-, N-ethyl-N-B-cyanoethyl-, N-ethyl-N-B-methoxyethyl-, N-ethyl-N-B-ethoxycarbonylethyl-, N-ethyl-N-B-amindocarbonylethy]- and N-ethy1-N-B-dimethyIaminoethyl-aniline, N,N-di-B- chloroethyl-, -di-,B-cyanoethyl-, -di-B-hydroxyethyland -di-B-methoxyethylaniline, N-methyl-N-alIyl-, N-methyl-N-cyclohexyl-, N-methyl-N-benzyl-, N-methyl-N-B-phenylethyL, N-methyl-N-phenyL, N-ethyl-N-phenyl-, N-B-chloroethyl-N-phenyL, N-B-cyanoethyl-N-phenyl-, N-methyl-N-4methylphenyl-, N-methyl-N-4-methoxy-phenyl-, N-ethyl-N-4- ethoxyphenyl-, and N-methyl-Nanaphthylaniline, N,N- dimethyland -diethyl-m-toludine, -m-anisidine and -m-phenetidine, m-chloroaniline, 3-dimethylamino-N- ethoxycarbonyl-aniline, 3-diethylamino-N- dimethylamidocarbonylaniline, 2-methyl-n-ethylaniline, 2-methoxy-N-isobutylaniline, 2,5-dimethoxy- N-ethyland -N,N-diethyl-aniline, diphenylamine, 2-

methyland 2-ethyl-diphenylamine, 4- methoxydiphenylamine, 2,2-diethyldiphenylamine, tetrahydroquinoline, N-methyl-, N-ethyI-, N-B- cyanethyl-tetrahydroquinoline, indoline, 2-methyl-, 2- phenyl-, 2,3-dimethyl-, 2,3,3-trimethyl-, l-methyl-, lethyl-, l-B-cyanoethyl-, l,2-dimethyl-, l,2,3-trimethyl-, and 1,2,3,3-tetramethyl-indoline, N-phenylpyrrolidine, N-phenylpiperdine, N-phenyl-morpholine, 'N-phenylpiperazine, carbazole, N-methyl-, N-ethyl-, N-B- cyanoethyl-, N-benzylcarbazole, N- methylphenothiazine, N-methylphenoxazine, I-N,N- dimethyland -diethylamino-naphthalene, 2-dimethylaminothiophene, Z-diemethylamino-thiazole, 2- dimethylamiano-4-phenylthiazole and 2-(phenylmethyl-amino)-thiazole.

Suitable compounds of the formula XV are, for example, anisole, phenetole, resorcinol-dimethyland -diethyl-ether, 3-methyl-anisole, B-naphthol, neroline and diphenyl-ether.

Suitable compounds of the formula XVI are, for exn-Butyl n-Butyl CH EH wherein R R and R have the meaning explained above. Suitable compounds of the formula XVIII are, for -cyanoethyl-indole, example, N-methyl-pyrrole, N-ethyl-, N-n-propyl-, N-iso-butyl-, N-phenyl, N-4-methoxyphenyl-, Nbenzyland N-cyclohexyl- 2,5-dimethyl-pyrrole, indole, N-methyl-, N-ethyland N-B-cyanoethyl-indole, Z-phenyI-indole, N-methyl-Z-phenyI-indole, 2-( a-thienyl )-indole, N-methyI-2-(a-thienyl-indole, 2-methyland 1,2- dimethyl-indole. The new dyestuffs are suitable for dyeing, printing and bulk dyeing materials which consist wholly or predominantly of poiymerised unsaturated nitriles such as acrylonitrile and vinylidene cyanide or of acidmodified polyesters or of acid-modified polyamides. They are furthermore suitable for the other known uses of cationic dyestuffs, such as dyeing and printing cellulose acetate, coir, jute, sisal and silk, tannin treated cotton and paper, for the manufacture of ball pen pastes and rubber-stamp inks, and for use in flexographic printing. The dyeings and prints on the materials initially mentioned, especially on polyacrylonitrile, are distinguished by their very high level of fastness, above all by very good fastness to light, wet processing, rubbing, decatising, sublimation and perspiration. A particular advantage of the new dyestuffs is their unusually high solubility in water and polar organic solvents; this permits the manufacture of stable, highly concentrated solutions. The dyestuffs are furthermore distinguished by their extraordinary uniform absorption, which permits the production of completely uniform dyeings in a simple manner.

The insensitivity of the solutions of the new dyestuffs towards extraneous ions, such as thiocyanate, cyanide, oxalate, sulphate, bromide, chlorozincate and others, which with the known cationic dyestuffs give precipitates which can noticeably interfere with the use of the dyestuffs, is particularly emphasised. Such interference can be entirely avoided or substantially reduced by the use of the dyestuffs according to the invention.

The parts mentioned in the examples are parts by weight; the temperatures are given in degrees Centigrade.

EXAMPLE 1 55 parts of the compound of the formula C2H5N and 30 parts of N,N-diethylaniline and 325 parts of phosphorus oxychloride, with the addition of 30 parts of phosphorus pentoxide, are stirred for about 8 hours at approx. 80. On cooling, a crystal paste results, which is poured into 2,000 parts of water. After complete hydrolysis of the phosphorus oxychloride, the resulting deep blue solution is neutralised with 350 parts of concentrated sodium hydroxide solution and additionally treated with 400 parts of sodium chloride.

which has separated out as crystals is filtered off and dried. The yield is approximately quantitative. On polyacrylonitrile, the dyestuff yields brilliant reddish-tinged blue dyeings and prints of very good fastness to light and to washing. The dyestuff is distinguished by very good solubility in cold water.

The starting product had been manufactured as follows:

23.6 parts of N-ethylnaphtholactam are introduced into l08 parts of chlorosulphonic acid at a temperature below 40, over the course of one hour. The batch is stirred for 30 minutes at 80 and after cooling to 30 is poured out onto 600 parts of ice. The sulphochloride which has precipitated is filtered 0H, washed with 30 parts of ice water and stirred in 75 parts of concentrated ammonia solution for 4 hours at 50 The batch is adjusted to pH 5 with 120 parts of 15% strength hydrochloric acid and the precipitate is illtered off and dried in vacuo at 29.6 parts of N- ethyl-4-sulphon-arnido-naphtholactam of melting point 2152l6 are obtained. 29.6 parts of N-ethyl-4-sulphonamido-naphtholactam in a solution of 16.7 parts of phosphorus oxychloride in 35.8 parts of dimethylformamide are stirred for 1 hour at room temperature.

The solution is poured into a mixture of 430 parts of lOpercent strength sodium chloride solution and parts of ice and the precipitate is filtered off and dried in vacuo at 70. 32.3 parts of 4-(N"-N"- dimethylformamidine-N'-sulph0nyl-)-N-ethylnaphtholactam of melting point l93l94 are obtained.

Instead of the N-ethyl-naphtholactam, the particular equivalent amount of N-methyl-, N-n-butyl-, N-isobutyl-, N-n-amyl-, N-iso-amyl-, N-B-chloroethyl-, N-B cyanoethyl-, N-B-methoxyethyL, N-B-methoxycarbonylethyl-, N-ethoxycarbonyl-methylor N- cyclohexyl-l,8-naphtholactam can also be employed. The compounds thus obtained on following the proce dure of Example 1 again yield very valuable dyestuffs or similar tinctorial properties.

If instead of the diethylaniline one of the following amines is used in the particular equivalent amount and in other respects the procedure remains unchanged, new dyestuffs are again obtained, which dye polyacrylonitrile in the colour shade indicated.

N-methyl-N-B-dimethylaminoethybaniline blue-violet N,N-dibenzyl-aniline do N,N-di-B-c anoeth l-aniline stron l y y reddish-t iri ged blue 2 methyl-N-iso-propyl-a.niline blue-violet 2.5-dimethoxy-N-ethyl-aniline greenitslh-tinged ue 2,5-diethox -N-methyl-aniline blue N-methyl- -c clohexyl-aniline do. N-meth l-N-aiiyl-aniline blue violet l-dime ylamino-naphthalene blue -Continued Amine Colour shade l-diethylanuno-naphthalene do. N-ethyl-N-B phenylethyl-aniline reddish-tinged blue N,N-di-B-phenylethyl-aniline do. N-ethyl-N-B-methoxycarbonylethyl-aniline do. N-methyl-N-B-n-butoxycarbonylethyl-aniline do. N-Ethyl-N-B-hydroxycarbonylethyl-aniline do. N-Ethyl-N-B-ethoxyethylaniline do. N-Ethyl-N-B-n-butoxyethyl-aniline do.

4-Methyl-3'-hydroxy-diphenylamine reddigh-tinged ue 4-Methyl-3-methoxy-diphenylamine do. 4,3'-Diethoxydiphenylamine do. N-Methyl-diphenylamine reddiah-tinged lue N-Ethyl-diphenylamine blue N-Methyl-4-methoxy-diphenylamine greenish tinged blue N-Ethyl-4-methoxy-diphenylamine do. N-Methyl-4-ethoxy-diphenylamine do. Triphenylamine strongly greenish-tinged blue 4.4'-Dimethoxy-triphenylamine strongly greenlue Carbazole red-violet N-Ethyl-earbazole violet Phenoxazine green N-B-Cyanoethyl-tetrahydro-quinoline blue N-Methyl-indoline do. N-Methyl-2-methyl-indoline do. N-Methyl-2-phenyl-indoline do. N-Phenyl-pyrrolidine do. N-Phenyl-piperidine do. N-Phenyl-morpholine reddialli-tinged EXAMPLE 2 34.3 g of the compound of the formula is obtained which on polyacrylonitrile gives bluishtinged red dyeings and prints of outstanding fastness.

If instead of indole the particular equivalent amount of l-methyl-, l-ethyl-, l-phenyl-, 1-benzyl-, l-,B- cyanoethyl-, l,2-dimethyl-, 2-methyl-, 2-phenyl-, 1-methyl-2-phenylor l-methyl 2-a-thienyl-indole, is used, new dyestuffs of corresponding structure, which are also outstandingly fast, are obtained.

EXAMPLE 3 66 parts of the compound of the formula (manufactured in accordance with the instructions in and dyes polyacrylonitrile in a blue colour of good fast- Example 1, using N,2-trimethylene-l ,8-naphtholactam as the starting product) and ll.7 parts of indole are warmed with 150 parts of chlorobenzene and 25 parts of phosphorus oxychloride for 6 hours to Thereafter the chlorobenzene is distilled off under reduced pressure. The residue is recrystallised from water. The dyestuff of the formula ness properties.

Instead of 1,3-diphenyl-pyrazoline, the particular equivalent amount of l-phenyl-3-methyl-, l-phenyl-3- (oz-thienyl l-phenyl-3-(4'-methoxyphenyl l-( 3 methyl-phenyl )-3-methyl-, l (-3 -methoxyphenyl )-3- phenyland l-(3', 6'-dimethoxyphenyl)-3-phenylpyrazoline-(AZ) can also be used.

,cri

CzH -N ="O separates out from the filtrate. On polyacrylonitrile, the dyestuff yields very fast green dyeings and prints.

Instead of the N-methyl-phenoxazine, the particular equivalent amounts of N-ethyl-, N-B-hydroxyethyl-. N-B-chloroethyl-, N-B- cyanoethyl N-B-methoxyethyl- N-B-dimethylamino-ethyl N-B-methoxycarbonylethyl-, N-B-hydroxycarbonylethyl-, N-allyl-, N-n-butyl or N(or l-),2,8-trimethyl-phenoxazine can also be employed. In that case, with the procedure otherwise unchanged, valuable green dyestuifs are again obtained.

and gives very fast blue dyeings and prints on polyacrylonitrile.

EXAMPLE 6 79 parts of the compound of the formula and 50 parts of N,N-di ethylaniline are stirred with 500 parts of phosphorus oxychloride and 50 parts of phosphorus pentoxide for hours at about 90. After cooling, the mixture is dissolved in 3,000 parts of water.

The dyestuff is separated out by adding 850 parts of concentrated sodium hydroxide solution and 300 parts of sodium chloride and is purified by recrystallisation from 4,000 parts of water, with the addition of active charcoal. It corresponds to the formula EXAMPLE 5 8.3 parts of the naphtholactam derivative used in Example 3 and 4.3 parts of diphenylamine are heated with 60 10 parts of phosphorus oxychloride and 6 parts of tin tetrachloride for 10 minutes to 130. The cooled mixture is treated with parts of methanol. After the solvolysis of the condensation agent is substantially comand gives very fast blue dyeings and prints on polyacrylonitrile.

The naphtholactam derivative used had been manufactured as follows:

170 parts of 1,8-naphtholactam and parts of powdered potassium hydroxide are stirred in 600 parts of dimethylforrnamide. 130 parts of benzyl chloride are added dropwise at 50 60 and the mixture is thereafplete, the mass is briefly boiled up. After cooling, the 5 ter stirred initially for 30 minutes at 60, then for 1 hour product is filtered off and the dyestuff, together with a second fraction obtained on distilling off the methanol, is recrystallised from water. It corresponds to the formula at and finally for 1 hour at ll0. After cooling, it is diluted with 3,000 parts of water and filtered, and the residue is washed with water and dried at about 60. 235.] parts of crude N-benzyl-naphtholactam, melting at between 104 and 108, are obtained. A sample recrystallised from alcohol melts at 120 122.

52 parts of N-benzylnaphtholactam are introduced into 220 parts of chlorosulphonic acid at room temperature. The batch is stirred for 2 hours at 30, poured into 2,000 parts of ice and filtered. The moist. residue is stirred in 200 parts of concentrated ammonia solution for 10 hours at room temperature and the mixture is rendered weakly acid with hydrochloric acid and filtered. The residue is washed with water and dried in vacuo at 70. 61 parts of N-benzyl-4-sulphonamidonaphtholactam of melting point 190 -l93 are obtained. 61 parts of N-benzyl-4- sulphonarnidonaphtholactam in a mixture of 180 parts of dimethylformamide and 36 parts of phosphorus oxychloride are stirred for 1 hour at room temperature. The batch is poured onto a mixture of 900 parts of 10% strength sodium chloride solution and 300 parts of water. The product is filtered off and dried in vacuo at a 70. 62 parts of 4-(N",N"dimethylformamidine-N- sulphonyl)-N-benzyl-naphtholactam are obtained. If

instead of dimethylformamide the corresponding amount of diethyl-, di-n-butyl-, N-methyl-N-B- cyanoethyl-, N-methyl-N-B-chloroethyl-, N-methyl-N-B-ethoxyethyl-, N-methyl-N-B- hydroxycarbonylethylformamide or N-formylpiperidine, -pyrrolidine, -piperazine or morpholine is used, the correspondingly substituted naphtholactam derivatives are obtained, which following the procedure of this example are again converted intovaluable blue dyestuffs of analogous structure.

EXAMPLE 7 A mixture of 7.5 parts of the compound of the formula 4.6 parts of 4-ethoxy-N-methyl-diphenylamine, 50 parts of phosphorus oxychloride and 3 parts of phosphorus pentoxide is stirred for 15 hours at about Thereafter, the excess condensation agent is decomposed by pouring the mixture into 300 parts of water whilst cooling. The dyestufl which hereupon separates out can be purified by recrystallisation from water. It corresponds to the formula EXAMPLE 8 39.9 parts of the compound of the formula and 21 parts of N,N-di-n-butyl-aniline are stirred with 500 parts of phosphorus oxychloride and 25 parts of anhydrous aluminium chloride for about 12 hours at Working-up is carried out in accordance with the instructions of Example 6. The dyestuff thus obtained corresponds to the formula CHZCHZCHZCH 3,853,913 27. 28 and on polyacrylonitrile gives very fast reddish-tinged EXAMPLE 9 blue dyeings and prints. The naphtholactam used had been manufactured as follows.

37.4 parts of the compound of the formula 55.2 parts of N-ethyl-4-sulphonamidonaphtholactam are stirred for 1 hour at 30 40 in a C H N C=O mixture of 28.2 parts of N-formyl-Nmethylcyclohexylamine and 200 parts of chloroform into which 20 1 parts of phosgene had previously been passed at room temperature. OH

The chlorofoml is distilled off and 400 parts of 10 O2 5 strength sodium chloride solution are added to the resi- 01-1 due. Theproduct is filtered off, washed with water and dried in vacuo at 70. The product is recrystallised from methanol/dimethylformamide. 42 parts of the compound of the first formula in Example 8, of melting 5 point 138 140, are obtained. If one of the naphand 17.7 parts of N,N-di-n-propyl-aniline together with tholactam derivatives listed in the table below and ob- 200 parts of phosphorus oxychloride and parts of tainable analogously is used instead of that mentioned zinc chloride are warmed to 90 100 for 20 hours. above, very valuable, tinctorially similar new dyestuffs Working-up in accordance with the instructions of Exare again obtained. 20 ample 6 yields the dyestuff of the formula 3:0 which on polyacrylonitrile gives very fast, blue dyeings and prints. The starting product had been manufactured as follows:

40 parts of phosphorus oxychloride are added at R 40 room temperature to 200 parts of tetramethylurea. 0 1 55.2 parts of N-ethyl-4-sulphamido-naphtholactam are 2 2 then added. The batch is stirred for 3 hours at 100 1 10 and poured onto 800 parts of water. The product is separated from the water and recrystallised from methanol/(1imethylformamide. Instead of tetrame- R R, R2

I thylurea, tetraethylurea, carbonyl-dl-pyrrolldlne, Methyl Methyl Methyl carbonyl-di-piperidine or -morpholine can also befigg l fi'l g I Egg A 1 used. The sulphonylguanidines thus obtainable can be meaty li't-Buly I {l-Buly I employed m the same way as the tetramethyl derivay so-amy so-amy Memoxycarbonylmemyl Methyi Methyl. 5O t ve, they also give valuable new dyestuffs with slmllar Ethoxycarbonylmethyl n-Butyl n-Bu'lyl unctonal p p Ethyl lso-propyl lso-propyl Ethyl Methyl Ethyl EXAMPLE l0 Ethyl Methyl n-But l Ethyl Methyl Cyclo exyl A solution of 30 parts of the compound of the for- Ethyl Methyl P enyl I Eth l Methyl Benzyl mu a Ethyl Methyl B- anoethyl Ethyl Methyl B-C loroethyl CH CH fl-a'eanoethyl Methyl Methyl N o 2 3 B- thoxycarbonylethyl Methyl Methyl \CH CH n-Prop l I Methyl Methyl 2 3 n-Buty Methyl Methyl n-Butyl Methyl n-Butyl nButyl v n-Propyl n-Propyl n-gutyl g fizihplllorpholine n- Ut T311116 Ming] R:+R2=NPE HydmXyethyl pipemine which was manufactured in a known manner by con- 33y] l Mgth l1 MeBthyll densatlon of 1,8-naphtholactam with dlethylanllme and nzy nuty nmy #Phmylethyl Memyl Methyl PhOSPhaOILUSYOJFYCShIOHdG and subsequent treatment w th aph l h l RfikFMorphonne excess a 1, in 00 parts of dry toluene, ls heated with ggglollexyl Methyl Methyl 20 parts of N-B-chloroethylsulphonyl-N',N'-dimethylg mgL formamldine to the boil for 2 3 hours. After cooling,

the dyestufi of the formula is filtered off and washed with benzene or cyclohexane. On polyacrylonitrile, the dyestufi-yields very brilliant, fast blue-violet dyeings and prints. If one of the compounds listed in the table which follows is used as the dyestuff base, valuable new dyestuffs are again obl and 27 parts of the aniline derivative of the formula tained. Instead of toluene, chlorobenzene can also be 0H used as the solvent.

together with 200 to 300 parts of phosphorus oxychloride and 20 parts of phosphorus pentoxide or phosphorus pentachloride are warmed at 90 for about 20 hours. The cooled mixture is poured into 2,000 parts of ice water. After completion of hydrolysis of the condensation agent, the dyestuff of the formula t OH w 5 O H N- -Q-I;I-CH CH aO N-CH N Cl Y Y1 R" R" Colour Shade Hydrogen Hydrogen Methyl Methyl Violet Hydrogen Hydrogen n-Propyl n-Propyl Blue-violet Hydrogen Hydrogen Methyl Phenyl Reddish-tinged blue Hydrogen Hydrogen Methyl Benz l Violet C lor ne Hydrogen Ethyl hy Reddish-tinged blue Chlor ne C lorine Ethyl Ethyl Reddish-tinged blue Brom ne Hydrogen Ethyl Ethyl Reddish-tinged blue Bromine Bromine Ethyl Etlgl Reddish-tinged blue Methoxy Hydrogen Ethyl 4- thoxyphenyl Greenish-tinged blue Hydrogen Ethyl Ethyl Ethyl Violet EXAMPLE ll is separated out by neutralising the strongly acid solution with sodium hydroxide solution and adding 200 parts of sodium chloride. The dyestuff gives fast reddish-tinged blue dyeings and prints on polyacrylonitrile.

lf instead of N-ethyl-4-bromo-l,8-naphtholactam, 33.1 parts of N-ethyl-4-dimethylfomiamidinosulphonyl-l,S-naphtholactam (Example 1) are used, the dyestuff of the formula which is also reddish-tinged blue, is obtained Correspending dyestuffs are obtained from the naphtholactam derivatives mentioned in Example 8 (Table).

EXAIVIPLE 12 'parts of l,3,3-trimethyl-2-methylene-indoline-waldehyde and 27 parts of the aniline derivative used in Example II are stirred-with 300 parts of chloroform 2 and parts of phosphorus oxychloride for 4 to 6 hours at the reflux temperature. The crude dyestuff which remains after distilling off the chloroform and the excess phosphorus oxychloride is purified by recrystallisation from water with the addition of active charcoal lt corresponds to the formula Ifi CH-CHQ-N CH3 and dyes polyacrylonitrile in very clear, bluish-tinged red shades. Instead of the abovementioned ail-aldehyde, the particular equivalent amount of 5-chloro-, 5- methyl-, 5-methoxy-, 5-methoxycarbonyl-, 7-methyl-, 7-ethyl-, 7-chloro-, 7-phenyl-, or 5,7-dichloro-l,3,3- trimethyl-2-methylene-w-aldehyde can also be used,

EXAMPLE 13 40.7 parts of the compound of the formula 4 O C H -N 0 and 23.6 g of diethylamino-carbanilic acid ethyl ester are warmed with 300 parts of phosphorus oxychloride for 15 hours to Thereafter the bulk of the phosphorus oxychloride is removed .under reduced pressure and the remainder is hydrolysed by stirring with v500 parts of water. The strongly acid solution is neutralised to pH 2 3 with sodium hydroxide solution at room temperature. The dyestuff filtered off after addition of about 50 parts of sodium chloride corresponds to the formula and dyes polyacrylonitrile in a fast blue colour. Instead of the abovementioned carbanilic acid ester, the following compounds can also be employed in the particuthe mixture is filtered and the residue is washed with 50 parts of methanol. 50 parts of the compound of the formula so -rhcri-oc ii,

of melting point 124 125 are obtained. 40 parts of this compound and 60 parts of N-methylbenzylamine are stirred for 2 hours at 50. The mixture is cooled to room temperature and the product is washed with methanol and dried in vacuo at 70. 47.2 parts of the compound of the first formula in Example l3, having a melting point of 180 -1 81, are obtained.

EXAMPLE 14 and gives outstandingly fast, blue dyeings and prints on polyacrylonitrile and acid-modified polyesters. If instead of 2-methoxy-diphenylamine the particular equivalent amount of 2,4-dimethoxy-, 2-ethoxy-, 2,5- diethoxy-, 2-methyl-, 2-ethylor 2,5-dimethyldiphenylamine is used, outstandingly fast new dyestuffs are again obtained.

EXAMPLE l 35.7 parts of the compound of the formula 0H2- (.111 Q2 S'N- C\N/ 0H2 l C H 3 and 22 parts of N-ethyl-N-B-cyanoethyl-aniline are stirred with 200 parts of phosphorus oxychloride for hours at about 90. Working-up takes place analogously to the instructions in Example 1. The dyestuff of the formula 0 H 5 0H CH ON (:1 4

CHTilH 0 8 N 0 CH 1? a CIH is obtained, which gives very fast, reddish-tinged blue dyeings and prints on polyacrylonitrile. The naphtholactam derivative used had been manufactured as follows: 5 27.6 parts of 4-sulphonamido-N-ethylnaphtholactam are dissolved in 70 parts of N-methyl-pyrrolidone. 15.6 parts of phosphorus oxychloride are added dropwise at 30 40. The batch is stirred for 3 hours at 100 and is poured into 800 parts of water. The product is filtered off and dried in vacuo at 70. The compound melts at 200 201.

EXAMPLE 16 31.7 parts of the compound of the formula CH O2S-N=CH-N/ 3 and 20 parts of N,N-diethylamine are heated with 300 350 parts of phosphorus oxychloride to 100 for about 10 hours. The cooled mixture is hydrolysed with about 1,000 parts of water and is then poured into excess aqueous ammonia solution. The dyestuff base thus obtained, of the formula is dissolved in toluene. The solution is dried azeotropithus obtained,of. 22.4 parts of dyestuff base in 500 parts of toluene is treated with 10 parts of dimethyl sulphate at and the mixture is kept at about 100 for 2 hours. After cooling, the quaternisation product is filtered off and washed with toluene or benzene. 1t corresponds to the formula CH S0 cally by distilling off a part of the solvent. A solution OCH-N :0

EXAMPLE l7 An aqueous dyebath containing, per litre, 0.75 g of 30% strength acetic acid, 0.40 g of sodium acetate and 0.25 g of the dyestufi of the formula is charged, at approx. C, with the amount of polyacrylonitrile fibres corresponding to a liquor ratio of l 40, heated to the boil over the course of 20 30 min-' utes and kept at this temperature for 30 60 minutes. After rinsing and drying the fibre, a brilliant, reddishtinged bluedyeing of very good fastness to light is obtained.

EXAMPLE l8 Acid-modified polyglycol terephthalate fibres of the type DACRON 64 (DuPont), or as described in Belgian Patent Specification 549,179 and US. Pat. No. 2,893,816, are introduced, in a liquor ration of l 40, into an aqueous bath at 20 which per litre contains 3' g of sodium sulphate, 0.5 2 g of an oleyl polyglycol ether mols of ethylene oxide), 2.5 5 g of diphenyl and 0.3 g of the dyestuff of the formula of Example 1, and which has been adjusted to a pl-l-value of 4.5 5.5 with acetic acid. The mixture is heated to 98 over the course of 30 minutes and the bath is kept at this temperature for minutes. Thereafter the fibres are rinsed and dried. A brilliant, reddish-tinged blue dyeing of very good fastness properties is obtained.

EXAMPLE l9 In a dyeing beaker of 500 ml capacity located in a heated waterbath, 0.75 g of the dyestuff of the formula of Example 1 are worked into a paste with a 20-fold amount of hot water, with the addition of a little acetic acid, and are dissolved by means of hot water. 0.5 g of the reaction product of 50 mols of ethylene oxide with 1 mol of oleyl alcohol are further added to the dyeing liquor, which is made up to 500 ml with cold water. The 6 pH-value of the dyeing liquor is adjusted to 4.5 5 with acetic acid or sodium acetate.

10 g of piece goods of acid-modified polyamide are constantly agitated in this dyeing liquor, whilst raising the temperature to 100C over the course of 15 minutes. Dyeing is carried out at the boil for 15 20 minutes and the material is rinsed with cold water and subsequently dried, for example by ironing or in a drying cabinet at 60 C. A material dyed reddish-tinged blue is obtained.

EXAMPLE 20 A A polyacrylonitrile fabric is printed with a printing paste of the following composition: 30 parts of the dyestuff of the formula of Example 1, 50 parts of thiodiethylene glycol, 30 parts of cyclohexanol, 30 parts of 30% strength acetic acid, 500 parts of crystal gum, 30 parts of aqueous zinc nitrate solution (d 1.5) and 330 parts of water.

The resulting print is dried, steamed for 30 minutes and subsequently rinsed. A brilliant, reddish-tinged blue print having very good fastness properties is obtained.

We claim:

1. A dyestuff of the formula CH O S-N=CH-'N 3 2. Dyestuff of the general formula R 22 O S-N=CH-N wherein R denotes alkyl of 1 to 4 carbon atoms;

R denotes alkyl of l to 4 carbon atoms;

R denotes alkyl of l to 5 carbon atoms;

R denotes methyl, ethyl, n-propyl, n-butyl;

R denotes methyl, ethyl, n-propyl, n-butyl', and

An represents an anion. k 

1. A DYESTUFF OF THE FORMULA
 2. Dyestuff of the general formula 